Alkoxyamines Containing a Radically Polymerizable Group

ABSTRACT

The instant invention relates to novel alkoxyamine initiators/regulators containing an ethylenically unsaturated, radically polymerizable group. The compounds are useful for the preparation of complex polymeric architectures. Further aspects of the invention are a polymerizable composition and a polymerization process comprising the alkoxyamine initiators/regulators, a macroinitiator obtainable by said polymerization process and a process for polymerizing with the macroinitiator.

The instant invention relates to novel alkoxyamine initiators/regulatorscontaining an ethylenically unsaturated, radically polymerizable group.The compounds are useful for the preparation of complex polymericarchitectures. Further aspects of the invention are a polymerizablecomposition and a polymerization process comprising the alkoxyamineinitiators/regulators, a macroinitiator obtainable by saidpolymerization process and a process for polymerizing with themacroinitiator.

Nitroxide mediated free radical polymerization (NMP) has been the objectof intensive academic and industrial research during the last years.Hawker et al., J. Am. Chem. Soc. 2003, 125, 3831-3838, for example,describe the use of nitroxide mediated free radical polymerization indesigning nanoscopic features of graft polymers. JP2003 268027 describesa polymeric alkoxyamine initiator useful for the preparation of block orgraft copolymers.

The control in NMP is due to the reversible capping of propagatingradicals with nitroxides to form the so-called dormant species. Thefield has been reviewed recently by Hawker C J, Bosman A W, Harth E,Chem. Rev. 101: 3661(2001). The originally widely used, readilyavailable, 2,2,6,6-tetramethyl-1-piperidinoxyl (TEMPO) works reasonablywell in styrene and its derivatives but is unsatisfactory for thecontrolled polymerization of other monomers such as acrylates. Superiorresults were obtained with recently developed cyclic nitroxides orrelated alkoxyamines derived from sterically highly hinderedpiperazinones, piperidines or 7-resp. 8-membered diazepanones asdescribed by Marque S, Sobek J, Fischer H, Kramer A, Nesvadba P,Wunderlich W, Macromolecules 36:3440 (2003). Other dasses aredioxathiazocanes or azopanones and azocanones. On the other hand,successful NMP of a broad range of monomers such as e.g. styrene,acrylates acryl amide, acrylonitrile, 1,3-dienes or maleic anhydride wasachieved with open-chain, β-hydrido nitroxides such asN-t-butyl-1-diethylphosphono-2,2-dimethylpropylnitroxide,N-t-butyl-isopropylphenylmethyl-nitroxide and the related alkoxyamines,and to a lesser extent with di-t-butyl-nitroxide (DTBN).

Besides of preparing simple homopolymers, synthesis of more complexpolymeric architectures is of high interest. Numerous examples have beendescribed. For instance WO 01/02345 and WO 03/004471 disclosemultifunctional alkoxyamines based on polyalkylpiperidines,polyalkylpiperazinones and polyalkylmorpholinones and their use for thepreparation of complex polymeric architectures such as e.g. starpolymers.

There is, however, still a need for new, easily available alkoxyamineinitiators useful for the preparation of complex polymeric architecturesstarting from a wide range of monomers, such as for example styrenic,acrylic, methacrylic and diene-type monomers. The instant inventionprovides alkoxyamines bearing, for example, acrylate or methacrylategroups. The conventional radical polymerization or copolymerization ofthese groups allows the preparation of macroinitiators which can be usedto make complex polymeric architectures, such as for exampleblock(co)polymers, comb(co)polymers, star(co)polymers,dendritic(co)polymers or hyperbranched(co)polymers.

One aspect of the invention is a compound of formula (I), (II) or (III)

wherein Q is

wherein

R is independently H or C₁-C₄alkyl;

D is O or NR₃;

in formula (I) m and n independently are a number 0 or 1 wherein atleast one of both is 1;

if in formula (I) m=0 and n=1

wherein

* denotes where the group is attached to the oxygen atom;

A is O or NR₃;

B₁ is C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups,C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring,which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or agroup —COO(C₁-C₁₈alkyl) or phenylene;

additionally -A-B₁- can be a direct bond; or

if A is —O— and D is NR₃, B₁ can be a direct bond; or

if A is NR₃ and D is O or NR₃, B₁ can be a direct bond;

E is a direct bond or a —C(O)— group;

R₁, R₂ and R₃ are independently H, C₁-C₁₈alkyl, which is unsubstitutedor substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl),C₅-C₇cycloalkyl, which is unsubstituted or substituted by C₁-C₈alkoxy,halogen or a group —COO(C₁-C₁₈alkyl), phenyl, which is unsubstituted orsubstituted by C₁-C₈alkoxy, C₁-C₈alkyl, halogen or a group—COO(C₁-C₁₈alkyl);

the group

is

A is as defined above; and

if A is O, E₁ is —CH₂—

if A is NR₃, E₁ is —C(O)—, —CH₂— or a direct bond;

R₄, R₅, R₆ are independently C₁-C₁₈alkyl, C₅-C₇cycloalkyl,C₇-C₉phenylalkyl or phenyl;

R₇, R₈ are independently H, C₁-C₁₈alkyl, C₅-C₇cycloalkyl,C₇-C₉phenylalkyl or C₁-C₁₈acyl;

L is a direct bond, O or NR₇;

R₉, R₁₀ are independently H or C₁-C₁₈alkoxy,

if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acylor N(R₃)₂; or

R₉ and R₁₀ together with the C-atom to which they are bonded form acyclic ketale group

wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or—CH₂—O—(C₁-C₁₈)acyl; or

R₉ and R₁₀ together form the group ═O, or ═N-A-R₇;

R₁₁, R₁₂, R₁₃ and R₁₄ are independently of each other C₁-C₄alkyl;

if in formula (I) m=1 and n=1

X is as defined above;

the group

is

wherein

A and B₁ are as defined above;

if in formula (I) m=1 and n=0

wherein A is O, NR₃ or a direct bond and E, R₁ and R₂ are as definedabove;

B₃ is H, C₁-C₂₅alkyl, which may be interrupted by O or NR₃ groups,C₅-C₇cycloalkyl, which can contain O and or NR₃ groups in the ring,which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or agroup —COO(C₁-C₁₈alkyl) or C₁-C₁₈alkoxy or phenyl;

the group

is

wherein

A and B₁ are as defined above;

in formula (II)

wherein

* denotes where X is attached to the oxygen atom and A, B₁, E, R₁ and R₂are as defined above;

the group

is

wherein A is as defined above;

L₁ is a divalent group derived from an aliphatic dicarboxylic acidhaving 2 to 18 carbon atoms from an aromatic dicarboxylic acid or froman aliphatic-aromatic dicarboxylic acid;

in formula (III)

X₁ is a group

wherein B₂ is a direct bond, C₁-C₂₅alkylene, which may be interrupted byO or NR₃ groups, C₅-C₇cycloalkylene which can contain O and or NR₃groups in the ring, which both are unsubstituted or substituted byC₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyI) or phenylene, whereinwhen B₂ is a direct bond one A is O and the other is NR₃;

A, B₁, R₁ and R₂ are as defined above and the group

is

C₁-C₁₈alkyl is a branched or unbranched radical, such as methyl, ethyl,propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1,3-dimethylbutyl,n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl,1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl,1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl.

C₁-C₂₅ alkylene is a branched or unbranched radical, such as methylene,ethylene, propylene, trimethylene, tetramethylene, pentamethylene,hexamethylene, heptamethylene, octamethylene, decamethylene,dodecamethylene, octadecamethylene or eicosamethylene. C₁-C₁₂alkyleneand, in particular, C₁-C₈alkylene are preferred.

C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups is, forexample, —CH₂—O—CH₂—, —CH₂—NH—CH₂—, —CH₂—N(CH₃)—CH₂—,—CH₂—O—CH₂CH₂—O—CH₂—, —CH₂—(O—CH₂CH₂—)₂O—CH₂—, —CH₂—(O—CH₂CH₂—)₃O—CH₂—or —CH₂—(O—CH₂CH₂—)₄O—CH₂—.

C₅-C₇cycloalkylene is a saturated hydrocarbon group having two freevalencies and at least one ring unit and is typically cyclopentylene,cyclohexylene or cycloheptylene. Cyclohexylene is preferred.

C₅-C₇cycloalkylene which can contain O and/or NR₃ groups in the ring arefor example following groups

Alkoxy of up to 8 carbon atoms is a branched or unbranched radical, suchas methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentoxy,isopentoxy, hexoxy, heptoxy or octoxy.

Halogen is typically chloro, bromo or iodo. Chloro is preferred.

C₅-C₇cycloalkylis cyclopentyl, cyclohexyl or cycloheptyl.

C₇-C₉Phenylalkyl which may be unsubstituted or substituted at the phenylmoiety by 1 to 3 C₁-C₄-alkyl is typically benzyl, α-methylbenzyl,α,α-dimethylbenzyl, 2-phenylethyl, 2-methylbenzyl, 3-methylbenzyl,4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or4-tert-butylbenzyl. Benzyl is preferred.

C₁-C₁₈acyl is for example benzoyl or C₁-C₁₈alkanoyl. Alkanoyl of up to18 carbon atoms is a branched or unbranched radical, typically formyl,acetyl, propionyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl,nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl,pentadecanoyl, hexadecanoyl, heptadecanoyl or octadecanoyl. Alkanoyl of2 to 12, e.g. of 2 to 6, carbon atoms is preferred. Acetyl isparticularly preferred.

A divalent group derived from an aliphatic dicarboxylic acid having 2 to18 carbon atoms is for example derived from oxalic acid, malonic acid,dimethylmalonic acid, succinic acid, pimelic acid, adipic acid,trimethyladipic acid, sebacic acid, azelaic acid and dimeric acids(dimerisation products of unsaturated aliphatic carboxylic acids such asoleic acid), alkylated malonic and succinic acids such asoctadecylsuccinic acid.

A divalent group derived from an aliphatic dicarboxylic acid having 2 to18 carbon atoms is for example derived from terephthalic acid,isophthalic acid, o-phthalic acid, and 1,3-, 1,4-, 2,6- or2,7-naphthalenedicarboxylic acid, 4,4′-diphenyidicarboxylic acid,4,4′-diphenylsulfonedicarboxylic acid, 4,4′-benzophenonedicarboxylicacid, 1,1,3-trimethyl-5-carboxyl-3-(p-carboxylphenyl)indane,4,4′-diphenyl ether dicarboxylic acid, bis-p-(carboxylphenyl)methane orbis-p-(carboxylphenyl)ethane.

For example in the compound of formula (I), (II) or (III)

Q is

wherein

R is independently H or C₁-C₄alkyl;

D is O or NR₃.

In a specific embodiment the compound is of formula (I), (II) or (III)

wherein Q is

wherein

R is independently H or C₁-C₄alkyl;

D is O or NR₃;

in formula (I) m and n independently are a number 0 or 1 wherein atleast one of both is 1;

if in formula (I) m=0 and n=1

wherein

* denotes where the group is attached to the oxygen atom;

A is O or NR₃;

B₁ is C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups,C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring,which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or agroup —COO(C₁-C₁₈alkyl) or phenylene;

additionally -A-B₁- can be a direct bond; or

if A is —O— and D is NR₃, B₁ can be a direct bond; or

if A is NR₃ and D is O or NR₃, B₁ can be a direct bond;

E is a direct bond or a —C(O)— group;

R₁, R₂ and R₃ are independently H, C₁-C₁₈alkyl, which is unsubstitutedor substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl),C₅-C₇cycloalkyl, which is unsubstituted or substituted by C₁-C₈alkoxy,halogen or a group —COO(C₁-C₁₈alkyl), phenyl, which is unsubstituted orsubstituted by C₁-C₈alkoxy, C₁-C₈alkyl, halogen or a group—COO(C₁-C₁₈alkyl);

the group

is

wherein

A is as defined above; and

if A is O, E₁ is —CH₂—

if A is NR₃, E₁ is —C(O)—, —CH₂— or a direct bond;

R₇ is H, C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₇-C₉phenylalkyl or C₁-C₁₈acyl;

R₉, R₁₀ are independently H or C₁-C₁₈alkoxy,

if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acylor N(R₃)₂; or

R₉ and R₁₀ together with the C-atom to which they are bonded form acyclic ketale group

wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or—CH₂—O—(C₁-C₁₈)acyl; or

R₉ and R₁₀ together form the group ═O, or ═N-A-R₇;

R₁₁, R₁₂, R₁₃ and R₁₄ are independently of each other C₁-C₄alkyl;

if in formula (I) m=1 and n=1

X is as defined above;

the group

is

wherein

A and B₁ are as defined above;

if in formula (I) m=1 and n=0

wherein A is O, NR₃ or a direct bond and E, R₁ and R₂ are as definedabove;

B₃ is H, C₁-C₂₅alkyl, which may be interrupted by O or NR₃ groups,C₅-C₇cycloalkyl, which can contain O and or NR₃ groups in the ring,which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or agroup —COO(C₁-C₁₈alkyl) or C₁-C₁₈alkoxy or phenyl;

the group

is

wherein

A and B₁ are as defined above;

in formula (II)

wherein

* denotes where X is attached to the oxygen atom and A, B₁, E, R₁ and R₂are as defined above;

the group

is

wherein A is as defined above;

L₁ is a divalent group derived from an aliphatic dicarboxylic acidhaving 2 to 18 carbon atoms from an aromatic dicarboxylic acid or froman aliphatic-aromatic dicarboxylic acid;

in formula (III)

X₁ is a group

wherein B₂ is a direct bond, C₁-C₂₅alkylene, which may be interrupted byO or NR₃ groups, C₅-C₇cycloalkylene which can contain O and or NR groupsin the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy,halogen or a group —COO(C₁-C₁₈alkyl) or phenylene, wherein when B₂ is adirect bond one A is O and the other is NR₃;

A, B₁, R₁ and R₂ are as defined above and

the group

is

Preference is given to compounds of formula (Ia)

wherein

Q is

wherein R is independently H or C₁-C₄alkyl;

wherein

* denotes where X is attached to the oxygen atom;

A is O or NR₃;

B₁ is C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups,C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring,which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or agroup —COO(C₁-C₁₈alkyl) or phenylene;

additionally -A-B₁- can be a direct bond; or

if A is —O— and D is NR₃, B₁ can be a direct bond; or

if A is NR₃ and D is O or NR₃, B₁ can be a direct bond;

E is a direct bond;

R₁, R₂ are H or CH₃;

R₃ is H, C₁-C₁₈alkyl, C₅-C₆cycloalkyl or phenyl;

the group

is

wherein

A is as defined above; and

if A is O, E₁ is —CH₂—

if A is NR₃, E₁ is —C(O)—, —CH₂— or a direct bond;

R₄, R₅, are methyl;

R₇, R₈ are independently H, C₁-C₁₈alkyl, C₅-C₇cycloalkyl, benzyl orC₁-C₁₈acyl;

L is a direct bond, O or NR₇;

R₉, R₁₀ are independently H or C₁-C₁₈alkoxy,

if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acylor N(R₃)₂; or

R₉ and R₁₀ together with the C-atom to which they are bonded form acyclic ketale group

wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or—CH₂—O—(C₁-C₁₈)acyl; or

R₉ and R₁₀ together form the group ═O, or ═N-A-R₇

R₁₁, R₁₂, R₁₃ and R₁₄ are independently of each other C₁-C₄alkyl.

For instance in the compounds of formula (Ia)

Q is

wherein R is H or C₁-C₄alkyl;

X is

wherein

* denotes where X is attached to the oxygen atom;

A is O or NR₃;

B₁ is C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups,C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring,which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or agroup —COO(C₁-C₁₈alkyl) or phenylene;

additionally -A-B₁- can be a direct bond; or

if A is —O— and D is NR₃, B₁ can be a direct bond; or

if A is NR₃ and D is O or NR₃, B₁ can be a direct bond;

E is a direct bond;

R₁, R₂ are H or CH₃;

R₃ is H, C₁-C₁₈alkyl, C₅-C₆cycloalkyl or phenyl;

the group

is

wherein

A is as defined above; and

if A is O, E₁ is —CH₂—

if A is NR₃, E₁ is —C(O)—, —CH₂— or a direct bond;

R₇ is H, C₁-C₁₈alkyl, C₅-C₇cycloalkyl, benzyl or C₁-C₁₈acyl;

R₉, R₁₀ are independently H or C₁-C₁₈alkoxy,

if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acylor N(R₃)₂; or

R₉ and R₁₀ together with the C-atom to which they are bonded form acyclic ketale group

wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or—CH₂—O—(C₁-C₁₈)acyl; or

R₉ and R₁₀ together form the group ═O, or ═N—O—R₇;

R₁₁, R₁₂, R₁₃ and R₁₄ are independently of each other C₁-C₄alkyl.

Special preference is given to compounds of formula (Ia)

wherein

Q is

X is

wherein

* denotes where X is attached to the oxygen atom;

A is O or NR₃;

B₁ is C₁-C₁₈alkylene, or phenylene;

R₁, R₂ are H or CH₃;

R₃ is H, C₁-C₄alkyl or phenyl;

the group

is

R₉, R₁₀ are independently H or C₁-C₁₈alkoxy, or

if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acylor N(R₃)₂; or

R₉ and R₁₀ together with the C-atom to which they are bonded form acyclic ketale group

wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or—CH₂—O—(C₁-C₁₈)acyl; or

R₉ and R₁₀ together form the group ═O, or ═N—O—R₇.

Particularly preferred are compounds of formula (Ia)

wherein

Q is

X is

wherein

* denotes where X is attached to the oxygen atom;

A is O or NR₃;

B₁ is C₁-C₄alkylene, or phenylene;

R₁, R₂ are H or CH₃;

R₃ is H, C₁-C₄alkyl or phenyl;

the group

is

Specific individual compounds are:

-   a) Acrylic acid    2-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy)-propionyloxy]-ethyl    ester-   b) Acrylic acid    2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionyloxy]-ethyl    ester-   c) Acrylic acid    2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-2-methyl-propionylamino]-ethyl    ester-   d) Acrylic acid    1-(1-{6-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionylamino]-hexylcarbamoyl}-ethoxy)-2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl    ester-   e) 2-Methyl-acrylic acid    2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionylamino]-ethyl    ester-   f) Acrylic acid    2-[2-(4-tert-butyl-2,2-diethyl-6,6-dimethyl-3-oxo-piperazin-1-yloxy)-propionylamino]-ethyl    ester-   g) Acrylic acid    2-(2-{N-teit-butyl-N-[1-(diethoxy-phosphoryl)-2,2-dimethyl-propyl]-aminooxy}-propionylamino)-ethyl    ester-   h) Acrylic acid    2-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionylamino]-ethyl    ester-   i) Terephthalic acid    bis-{1-[1-(2-acryloyloxy-ethylcarbamoyl)-ethoxy]-2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl}ester-   j) 2-Methyl-acrylic acid    2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionyloxy]-ethyl    ester-   k) 2-Methyl-acrylic acid    1-[1-(2-acryloyloxy-ethoxycarbonyl)-ethoxy]-2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl    ester-   l) Acrylic acid    2-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionyloxy]-ethyl    ester-   m) Acrylic acid    2-{(2-acryloyloxy-ethyl)-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionyl]-amino}-ethyl    ester.

The compounds of the present invention have all an ethylenicallyunsaturated bond and in addition a —O—N< group. They can therefore beused as monomers in a conventional radical polymerization process,preferably together with further ethylenically unsaturated monomers andas initiators/regulators in controlled radical polymerization processes.

Both processes can be carried out independently of each other or in aconsecutive manner.

When the compounds of the present invention are used in a controlledpolymerization process, the resulting polymer or copolymer has typicallya polydispersity index of 1.0 to 2.0, preferably from 1.1 to 1.7 and inparticular from 1.1 to 1.5.

A further aspect of the invention is a polymerizable compositioncomprising

-   -   a) at least one ethylenically unsaturated monomer;    -   b) a radical polymerization initiator; and    -   c) a compound of formula (I), (II) or (III) as described above.

The ethylenically unsaturated monomer of component a) can be chosen froma variety of monomers. Such as isoprene, 1,3-butadiene, α-C₅-C₁₈alkene,styrene, α-methyl styrene, p-methyl styrene p-tert-butyl-styrene or acompound of formula CH₂═C(R_(a))—(C=Z)-R_(b), wherein R_(a) is hydrogenor C₁-C₄alkyl, R_(b) is NH₂, O⁻(Me⁺), unsubstituted C₁-C₁₈alkoxy,C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom, orhydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;

Me is a monovalent metal atom or the ammonium ion.

Z is oxygen or sulfur.

Examples for R_(a) as C₂-C₁₀₀alkoxy interrupted by at least one O atomare of formula

wherein R_(c) is C₁-C₂₅alkyl, phenyl or phenyl substituted byC₁-C₁₈alkyl, R_(d) is hydrogen or methyl and v is a number from 1 to 50.These monomers are for example derived from non ionic surfactants byacrylation of the corresponding alkoxylated alcohols or phenols. Therepeating units may be derived from ethylene oxide, propylene oxide ormixtures of both.

Further examples of suitable acrylate or methacrylate monomers are givenbelow.

An⁻, wherein An⁻ and R_(a) have the meaning as defined above and R_(e)is methyl, benzyl or benzoylbenzyl. An⁻ is preferably Cl⁻, Br⁻ or—O₃S—O—CH₃.

Further acrylate monomers are

Me⁺, Me⁺ is an alkali metal cation or the ammonium cation.

Examples for suitable monomers other than acrylates are

Preferably R_(a) is hydrogen or methyl, R_(b) is NH₂, gycidyl,unsubstituted or with hydroxy substituted C₁-C₄alkoxy, unsubstitutedC₁-C₄alkylamino, di(C₁-C₄alkyl)amino, hydroxy-substitutedC₁-C₄alkylamino or hydroxy-substituted di(C₁-C₄alkyl)amino; and

Z is oxygen.

For example the ethylenically unsaturated monomer is selected from thegroup consisting of ethylene, propylene, n-butylene, i-butylene,styrene, substituted styrene, conjugated dienes, acrolein, vinylacetate, vinylpyrrolidone, vinylimidazole, maleic anhydride,(alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylicesters, (alkyl)acrylonitriles, (alkyl)acrylamides, vinyl halides orvinylidene halides.

For instance the ethylenically unsaturated monomer is styrene,substituted styrene, methylacrylate, ethylacrylate, butylacrylate,isobutylacrylate, tert. butylacrylate, hydroxyethylacrylate,hydroxypropylacrylate, dimethylaminoethylacrylate, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, hydroxyethyl(meth)acrylate,hydroxypropyl(meth)acrylate, dimethylaminoethyl(meth)acrylate,acrylonitrile, methacrylonitrile, acrylamide, methacrylamide ordimethylaminopropyl-methacrylamide.

Very suitable monomers are for example styrene, C₁-C₈alkylesters ofacrylic or methacrylic acid, such as n-butylacrylate or methacrylate,acrylonitrile or methacrylonitrile, in particular styrene, acrylonitrileand n-butylacrylate.

It is also possible to use mixtures of the afore mentioned monomers, inparticular styrene/acrylonitrile, styrene/butylacrylate,styrene/methylmethacrylate and styrene/butylmethacrylate.

Preference is given to a polymerizable composition wherein theethylenically unsaturated monomer is a compound of formulaCH₂═C(R_(a))—(C=Z)-R_(b), wherein Z is O or S;

R_(a) is hydrogen or C₁-C₄alkyl;

R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy,C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom, orhydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino,di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino orhydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or—O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻;

An⁻ is a anion of a monovalent organic or inorganic acid;

Me is a monovalent metal atom or the ammonium ion.

For example the the radical polymerization initiator, component b) is aazo compound, a peroxide, a perester or a hydroperoxide.

Specific preferred radical initiators are 2,2′-azobisisobutyronitrile,2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile,dimethyl-2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile,2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane),2,2′-azobis(N,N′-dimethyleneisobutyramidine), free base orhydrochloride, 2,2′-azobis(2-amidinopropane), free base orhydrochloride,2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide;acetyl cyclohexane sulphonyl peroxide, diisopropyl peroxy dicarbonate,t-amyl perneodecanoate, t-butyl perneodecanoate, t-butyl perpivalate,t-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoylperoxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide,bis(2-methylbenzoyl) peroxide, disuccinic acid peroxide, diacetylperoxide, dibenzoyl peroxide, t-butyl per 2-ethylhexanoate,bis-(4-chlorobenzoyl)-peroxide, t-butyl perisobutyrate, t-butylpermaleinate, 1,1-bis(t-butylperoxy)3,5,5-trimethylcyclohexane,1,1-bis(t-butylperoxy)cyclohexane, t-butyl peroxy isopropyl carbonate,t-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, t-butylperacetate, t-amyl perbenzoate, t-butyl perbenzoate, 2,2-bis(t-butylperoxy) butane, 2,2 bis(t-butylperoxy) propane, dicumylperoxide, 2,5-dimethylhexane-2,5-di-t-butylperoxide, 3-t-butylperoxy3-phenylphthalide, di-t-amyl peroxide, α,α′-bis(t-butylperoxy isopropyl)benzene, 3,5-bis(t-butylperoxy)3,5-dimethyl 1,2-dioxolane, di-t-butylperoxide, 2,5-dimethylhexyne-2,5-di-t-butylperoxide,3,3,6,6,9,9-hexamethyl 1,2,4,5-tetraoxa cyclononane, p-menthanehydroperoxide, pinane hydroperoxide, diisopropylbenzenemono-α-hydroperoxide, cumene hydroperoxide or t-butyl hydroperoxide.

A further aspect of the invention is a process for preparing anoligomer, a cooligomer, a polymer or a copolymer (block, random orgraft) by free radical polymerization of at least one ethylenicallyunsaturated monomer or oligomer, which comprises (co)polymerizing themonomer or monomers/oligomers in the presence of

-   -   a) a free radical initiator; and    -   b) a compound of formula (I), (II) or (III) as described above.

The polymerization is carried out by applying heat or electromagneticradiation from microwaves to γ-radiation.

The polymerization is usually carried out under atmospheric pressure forexample for 10 minutes to 16 hours, preferably from 1 hour to 8 hours.

Typically the polymerization is carried out by heating and takes placeat a temperature between 0° C. and 160° C., for example between 20° C.and 160° C., for instance between 50° C. and 140° C.

The amount of component b) may vary in a wide range, for example from 1%to 100% by weight, based on the weight of the sum of all ethylenicallyunsaturated compounds. In many cases 10% to 70% are desirable.

The radical polymerization process as such is known and may be carriedout in bulk, in the presence of an organic solvent or in the presence ofwater or in mixtures of organic solvents and water. Additionalcosolvents or surfactants, such as glycols or ammonium salts of fattyacids, may be present. Other suitable cosolvents are describedhereinafter.

If organic solvents are used, suitable solvents or mixtures of solventsare typically pure alkanes (hexane, heptane, octane, isooctane),aromatic hydrocarbons (benzene, toluene, xylene), halogenatedhydrocarbons (chlorobenzene), alkanols (methanol, ethanol, ethyleneglycol, ethylene glycol monomethyl ether), esters (ethyl acetate,propyl, butyl or hexyl acetate) and ethers (diethyl ether, dibutylether, ethylene glycol dimethyl ether), anisol, tert-butyl-benzene ormixtures thereof.

When the above described polymerization has been carried out, a polymeror oligomer is obtained, which has attached several —O—N< groups at thepolymer backbone. These groups can be used to carry out a controlledradical polymerization starting from the various initiating radicals atthe polymer backbone and complex polymer architectures ca be obtained.

Consequently a further aspect of the invention is a polymeric oroligomeric macroinitiator obtainable by a process as described above.

Also an aspect of the invention is a process for preparing a comb, star,tapered or branched polymer or copolymer by controlled free radicalpolymerization (CFRP), which comprises polymerizing at least oneethylenically unsaturated monomer in the presence of the polymericmacroinitiator obtainable in a process as described above.

Typically the polymerization process is carried out by heating and takesplace at a temperature between 80° C. and 160° C.

A further aspect is the use of a polymeric macroinitiator obtainable ina process as described above as radical initiator for the polymerizationof ethylenically unsaturated monomers.

The definitions and preferences given for the compounds of formula (I),(II) and (III) apply also for the other aspects of the invention.

The polymers prepared by the present invention are useful for followingapplications:

adhesives, detergents, dispersants, emulsifiers, surfactants, defoamers,adhesion promoters, corrosion inhibitors, viscosity improvers,lubricants, rheology modifiers, thickeners, crosslinkers, papertreatment, water treatment, electronic materials, paints, coatings,photography, ink materials, imaging materials, superabsorbants,cosmetics, hair products, preservatives, biocide materials or modifiersfor asphalt, leather, textiles, ceramics and wood.

Because the present polymerization is a “living” polymerization, it canbe started and stopped practically at will. Furthermore, the polymerproduct retains the functional alkoxyamine group allowing a continuationof the polymerization in a living matter. Thus, in one embodiment ofthis invention, once the first monomer is consumed in the initialpolymerizing step a second monomer can then be added to form a secondblock on the growing polymer chain in a second polymerization step.Therefore it is possible to carry out additional polymerizations withthe same or different monomer(s) to prepare multi-block copolymers.

The following examples illustrate the invention

PREPARATION EXAMPLES A1-A13 Example A1 Acrylic acid2-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy)-propionyioxy]-ethylester (Compound 1, Tab. 1)

A) Acrylic acid 2-(2-bromo-propionyloxy)-ethyl ester

The synthesis of acrylic acid 2-(2-bromo-propionyloxy)-ethyl ester isconducted as reported in Macromolecules, 1197, 30, 5192-94.

B) Compound 1, Tab. 1

To a stirred solution of 99.6 g (0.46 mol) of2,6-diethyl-1-hydroxy-2,3,6-trimethyl-piperidin-4-one (prepared asdescribed in U.S. Pat. No. 6,353,107 B1, example 2), 66.3 g (0.46 mol)of CuBr and 29.4 g (0.46 mol) Cupper in 1000 ml toluene 160 g (0.92 mol)of N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDTA) are added. Thebrown suspension is then cooled to 10° C. and 116 g (0.46 mol) ofacrylic acid 2-(2-bromo-propionyloxy)-ethyl ester dissolved in 250 mltoluene are added dropwise while keeping the temperature below 15° C.The reaction mixture is stirred for another 12 h at room temperature andthen filtered. The filtrate is washed with water (3×500 ml), then with a10% solution of EDTA (3×500 ml), dried over NaSO₄ and evaporated. Theresidue is chromatographed over Silica gel with hexane-ether (7:3) toafford 165 g of the title compound as slightly yellow oil.

Elemental analysis calculated for C₂₀H₃₅NO₆: C, 62.31%; H, 9.15%; N,3.63%. Found: C, 62.31%; H, 9.28%; N, 3.58%.

Example A2 Acrylic acid2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionyloxy]-ethylester (Compound 2, Tab. 1)

In analogy to Example 1B) are reacted: 42.46 g (0.20 mol)2,6-diethyl-1-oxy-2,3,6-trimethylpiperidin-4-one, 50.22 g (0.20 mol)acrylic acid 2-(2-bromo-propionyloxy)-ethyl ester, 28.7 g (0.20 mol)CuBr, 12.7 g (0.20) Cupper and 69.3 g (0.40 mol) PMDTA to afford 54.8 gof the title compound as a colorless oil.

Elemental analysis calculated for C₂₀H₃₃NO₆: C, 62.64%; H, 8.67%; N,3.65%. Found: C, 62.32%; H, 8.79%; N, 3.66%.

Example A3: Acrylic acid2-[2-(2.6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-2-methyl-propionylamino]-ethylester (Compound 3, Tab. 1)

B) 2-Bromo-N-(2-hydroxy-ethyl)-2-methyl-propionamide

To a stirred solution of 12.2 g (0.2 mol) of ethanolamine in 50 mltetrahydrofurane (THF) are at 0° C. added 23.0 g (0.1 mol) ofα-isobutyrylbromide. The mixture is then stirred 12 h at roomtemperature and the THF is then evaporated. To the residue are added 20ml of water and 7 g of NaCl. The mixture is extracted with 25 ml of eacht-butyl-methyl ether and ethylacetate, the extracts are washed withbrine, dried over MgSO₄ and evaporated to afford 19.9 g of the titlecompound as a colorless oil.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 7.17 (bs, 1H), 3.76 (t, 2H), 3.46 (m,2H), 2.79 (bs, 1H), 1.96 (s, 6H).

C)2-(2,6-Diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-N-(2-hydroxy-ethyl)-2-methyl-propionamide

To a stirred solution of 13.85 g (0.066 mol) of2-bromo-N-(2-hydroxy-ethyl)-2-methyl-propionamide and 12.74 g (0.06 mol)of 2,6-diethyl-1-oxy-2,3,6-trimethyl-piperidin-4-one (prepared asdescribed in U.S. Pat. No. 6,353,107 B1, example 3) in ethylacetate (50ml) are under argon added 11.8 g (0.12 mol) CuCl. To the stirredsuspension are added dropwise 20.8 g (0.12 mol) of N,N,N′, N″,N″-pentamethyidiethylenetriamine (PMDTA) while keeping the temperaturebelow 35° C. The mixture is stirred for another 4 h at room temperatureand then filtered. The filtrate is washed with water (3×50 ml), thenwith 1% solution of EDTA, dried over MgSO₄ and evaporated. The residueis chromatographed over Silica gel with hexane-ethylacetate (1:1 to 1:3)to afford 17.5 g of the title compound as a colorless oil.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 6.87-6.86 (bs, 1H), 3.73 (m, 2H),3.47-3.41 (m, 2H), 2.85-0.80 (m, 29H).

D) Compound 3, Tab. 1

Acryloylchloride (1.67 g, 0.0185 mol) is added dropwise and below 40° C.to a solution of 6.22 g (0.018 mol) of the intermediate prepared underB) and 2.6 ml (0.01852 mol) triethylamine in 30 ml of toluene.Additional 1.2 ml of triethylamine and 0.6 ml of acryloylchloride areadded after 2.5 h. The mixture is stirrred for 1 h, then washed with4×10 ml water, dried over MgSO₄ and evaporated. Chromatography of theresidue over silica gel with hexane-ethyl acetate (2:1) afford 6.45 g ofthe title compound as a viscous colorless oil.

MS (APCI): calculated C₂₁H₃₆N₂O₅ (396.53). found M⁺=396.

Example A4 Acrylic acid1-(1-{6-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionylamino]-hexylcarbamoyl}-ethoxy)-2,6-diethyl-2,3,6-trimethyl-piperidin-4-ylester (Compound 4, Tab. 1)

Acryloylchloride (0.27 g, 3.0 mmol) is added dropwise and below 20° C.to a solution of 0.98 g (1.5 mmol) of2-(2,6-Diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy)-N-{6-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy)-propionylamino]-hexyl}-propionamide(prepared as described in WO 03/004471 A1, example A3) and 0.3 g (3.0mmol) triethylamine in 30 ml ethyl acetate. The mixture is stirred for12 h at room temperature, then washed with 3×10 ml water, dried overNa₂SO₄ and evaporated. Chromatography of the residue over silica gelwith hexane-ethyl acetate (3:2) afford 0.33 g of the title compound as aviscous slightly yellow oil.

MS (APCI): calculated C₄₂H₇₄N₄O₈ (763.08). found M⁺=762.55.

Example 5 2-Methyl-acrylic acid2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionylamino]-ethylester (Compound 5, Tab. 1)

A) 2-Chloro-N-(2-hydroxy-ethyl)-propionamide

Ethanolamine (13.45 g, 0.22 mol) is added to 21.5 ml (0.2 mol) of2-chloropropionic acid methylester. The mixture solidifies afterstanding at room temperature for 60 h. The solid is triturated withethylacetate, the crystals are filtered off and dried to afford 27.75 gof the title compound as white crystals, mp. 64° C.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 7.09 (bs, 1H), 4.44 (q, 1H), 3.76 (t,2H), 3.48 (m, 2H), 2.79 (bs, 1H), 1.75 (d. 3H).

B)2-(2,6-Diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-N-(2-hydroxy-ethyl)-propionamide

In analogy to Example 3B) were reacted: 30.35 g (0.143 mol)2,6-diethyl-1-oxy-2,3,6-trimethyl-piperidin-4-one, 24.35 g (0.157 mol)2-chloro-N-(2-hydroxy-ethyl)-propionamide, 28.3 g (0.286 mol) CuCl and49.55 g (0.286 mol) PMDTA to afford 44.8 g of the title compound as acolorless resin.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 6.80 (bs, 1H), 4.40 (m, 1H), 3.76-0.90(m, 30H).

C) Compound 5, Tab. 1

In analogy to Example 3C) are reacted: 15.76 g (0.024 mol)2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-N-(2-hydroxy-ethyl)-propionamide,3.0 g (0.028 mol) methacryloyl-chloride and 4.2 ml triethylamine toafford 6.08 g of the title compound as a colorless resin.

MS (APCI): calculated C₂₁H₃₆N₂O₅ (396.53). found M⁺=396.

Example 6 Acrylic acid2-[2-(4-tert-butyl-2,2-diethyl-6,6-dimethyl-3-oxo-piperazin-1-yloxy)-propionylamino]-ethylester (Compound 6, Tab. 1)

A)2-(4-tert-Butyl-2,2-diethyl-6,6-dimethyl-3-oxo-piperazin-1-yloxy)-N-(2-hydroxy-ethyl)-propionamide

In analogy to Example 3B) are reacted 5.0 g (0.033 mol)2-chloro-N-(2-hydroxy-ethyl)-propionamide, 10.4 g (0.033 mol) PMDETA,5.94 g (0.06 mol) CuCl and 7.66 g (0.03 mol)1-tert-butyl-3,3-diethyl-4-oxy-5,5-dimethyl-piperazin-2-one (prepared asdescribed in U.S. Pat. No. 6,479,608 B1) to afford 9.18 g of the titlecompound as a colorless resin.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 7.28 (bs, 1H), 4.30 (q, 1H), 3.77 (m,2H), 3.47 (m, 2H), 3.08 (bs, 1H), 2.0-0.93 (m, 30H).

B) Compound 6, Tab. 1

In analogy to Example 3C) are reacted 7.68 g (0.0207 mol),2-(4-tert-butyl-2,2-diethyl-6,6-dimethyl-3-oxo-piperazin-1-yloxy)-N-(2-hydroxy-ethyl)-propionamide2.1 g (0.023 mol) acryloylchloride and 3.4 ml (0.023 mol) triethylamineto afford 6.75 g of the title compound as a colorless resin.

MS (APCI): calculated C₂₂H₃₉N₃O₅ (425.57). found M⁺=425.

Example 7 Acrylic acid2-(2-{N-tert-butyl-N-[1-(diethoxy-ghosphoryl)-2,2-dimethyl-propyl]-aminooxy}-propionylamino)-ethylester (Compound 7, Tab. 1)

A)(1-{tert-Butyl-[1-(2-hydroxy-ethylcarbamoyl)-ethoxy]-amino}-2,2-dimethyl-propyl)-phosphonicacid diethyl ester

In analogy to Example 3B) are reacted 9.7 g (0.056 mol) PMDTA, 5.54 9(0.056 mol) CuCl, 4.7 g (0.031 mol)2-chloro-N-(2-hydroxy-ethyl)-propionamide and 8.3 g (0.028 mol)[1-tert-butyl-amino-N-oxyl)-2,2-dimethyl-propyl]-phosphonic acid diethylester (prepared as described by P. Tordo et al.: Macromolecules 33. 1141(2000)) to afford 9.9 g of the title compound as a colorless oil.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 8.56 (bs, 1H), 4.70-3.20 (m, 11H),2.10-1.0 (m, 27H).

C) Compound 7, Tab. 1

In analogy to Example 3C) are reacted 8.43 g (0.0205 mol)(1-{tert-butyl-[1-(2-hydroxy-ethylcarbamoyl)-ethoxy]-amino}-2,2-dimethyl-propyl)-phosphonicacid diethyl ester, 2.08 g (0.025 mol) acryloylchloride and 3.2 ml(0.025 mol) triethylamine to afford the title compound as twodiastereomers: 4.79 g of a colorless oil and 3.5 g of a white solid, mp95-98° C.

The MS (APCI) of each isomer: M⁺=464, for C₂₁H₄₁N₂O₇ calculatedM=464.54.

Example 8 Acrylic acid2-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionylamino]-ethylester (Compound 8, Tab. 1)

A)2-(2,6-Diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy)-N-(2-hydroxy-ethyl)-propionamide

In analogy to Example 3B) are reacted 11.1 g (0.064 mol) PMDTA, 6.33 g(0.064 mol) CuCl, 5.33 g (0.07 mol)2-chloro-N-(2-hydroxy-ethyl)-propionamide and 7.72 g (0.032 mol)2,6-diethyl-2,3,6-trimethyl-piperidine-1-oxyl (prepared as described inU.S. Pat. No. 6,353,107 B1, example 2) to afford 11.57 g of the titlecompound as a colorless oil.

B) Compound 8, Tab. 1

In analogy to Example 3C) are reacted 8.25 g (0.025 mol)2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy)-N-(2-hydroxy-ethyl)-propionamide,7.8 ml (0.056 mol) triethylamine and 5.0 g (0.055 mol) acryloylchlorideto afford 7.5 g of the title compound as a colorless resin.

MS (APCI): calculated C₂₃H₃₈N₂O₆ (438.57). found M⁺=438.

Example 9 Terephthalic acidbis-{1-[1-(2-acryloyloxy-ethylcarbamoyl)-ethoxy]-2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl}ester(Compound 9, Tab. 1)

a. A) Terephthalic acidbis-(2,6-diethyl-1-oxyl-2,3,6-trimethyl-piperidin-4-yl) ester

To a solution of 25.72 g (0.12 mol)2,6-diethyl-2,3,6-trimethyl-piperidine-1-oxyl in 30 ml pyridine and 80ml dichloromethane are added 12.2 g (0.06 mol) terephthaloylchloride and0.3 g 4-dimetylaminopyridine. The mixture after 72 h stirring at roomtemperature is diluted with 100 ml dichloromethane and washed with water(3×50 ml). The organic phase is dried over MgSO₄, evaporated andchromatographed on silica gel with hexane-ethylacetate (4:1) to afford31.85 g of the title compound as a red resin.

B) Terephthalic acidbis-{2,6-diethyl-1-[1-(2-hydroxy-ethylcarbamoyl)-ethoxy]-2,3,6-trimethyl-piperidin-4-yl}ester

In analogy to Example 3B) are reacted 10.4 g (0.06 mol) PMDTA, 5.94 g(0.06 mol) CuCl, 5.0 g (0.033 mol)2-chloro-N-(2-hydroxy-ethyl)-propionamide and 8.38 g (0.015 mol)terephthalic acidbis-(2,6-diethyl-1-oxyl-2,3,6-trimethyl-piperidin-4-yl) ester to afford6.25 g of the title compound as a colorless resin.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 8.1 (bs, 4ArH), 6.8-6.6 (m, 2H), 5.6-3.3(m, 14H), 2.6-0.7(m, 50H).

C) Compound 9, Tab. 1

In analogy to Example 3C) are reacted 6.0 g (0.0076 mol) terephthalicacidbis-{2,6-diethyl-1-[1-(2-hydroxy-ethylcarbamoyl)-ethoxy]-2,3,6-trimethyl-piperidin-4-yl}ester,2.65 ml (0.0091 mol) triethylamin and 1.65 g (0.0091 mol)acryloylchloride to afford 4.5 g of the title compound as a colorlessresin.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 8.1 (bs, 4ArH), 6.8-3.3 (m, 20H),2.4-0.7(m, 50H).

Example 10 2-Methyl-acrylic acid2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionyloxy]-ethylester (Compound10. Tab. 1)

In analogy to Example 1B) are reacted: 10.61 g (0.05 mol)2,6-diethyl-1-oxy-2,3,6-trimethyl-piperidin-4-one, 13.25 g (0.05 mol)2-methyl-acrylic acid 2-(2-bromo-propionyloxy)-ethyl ester, 9.89 g (0.1mol) CuCl and 17.33 g (0.1 mol) PMDTA to afford 16.0 g of the titlecompound as a yellow oil.

MS (APCI): calculated C₂₁H₃₅NO₆ (397.52). found M⁺=397.

Example 11 2-Methyl-acrylic acid1-[1-(2-acryloyloxy-ethoxycarbonyl)-ethoxy]-2,6-diethyl-2,3,6-trimethyl-piperidin-4-ylester (Compound 11, Tab. 1)

In analogy to Example 4) are reacted 2.5 g (6.5 mmol) of compound 1(fromExample 1B), 0.73 g (7.2 mmol) triethylamine and 0.75 g (7.2 mmol)methacryloylchloride to afford 1.4 g of the title compound as acolorless oil.

MS (APCI): calculated C₂₄H₃₉NO₇ (453.58). found M⁺=453.

Example 12 Acrylic acid2-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionyloxy]-ethylester (Compound 12, Tab. 1)

In analogy to Example 4) are reacted 2.5 g (6.5 mmol) of compound 1(fromExample 1B), 0.73 g (7.2 mmol) triethylamine and 0.65 g (7.2 mmol)acryloylchloride to afford 1.6 g of the title compound as a colorlessoil.

MS (APCI): calculated C₂₃H₃₇NO₇ (439.55). found M⁺=439.

Example 13 Acrylic acid2-{(2-acryloyloxy-ethyl)-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionyl]-amino}-ethylester (Compound13, Tab. 1)

A) 2-Chloro-N,N-bis-(2-hydroxy-ethyl)-propionamide

Diethanolamine (10.51 g, 0.1 mol) is added to 12.25 (0.1 mol) of2-chloropropionic acid methylester. The mixture is stirred for 24 h atroom temperature. The formed methanol is evaporated to afford 18.8 g ofthe title compound as slightly yellow oil.

¹H-NMR (300 MHz, CDCl₃, δ ppm): 4.84 (q, 1H), 4.0-3.3 (m, 10H), 1.68 (d.3H).

B) Acrylic acid2-[(2-acryloyloxy-ethyl)-(2-chloro-propionyl)-amino]-ethyl ester

In analogy to Example 4) are reacted 17.0 g (0.087 mol) of2-chloro-N,N-bis-(2-hydroxy-ethyl)-propionamide, 19.4 g (0.19 mol)triethylamine and 17.32 g (0.19 mol) acryloylchloride to afford 8.2 g ofthe title compound as a yellow oil. TABLE 1 Nr Structure 1

2

3

4

5

6

7

8

9

10

11

12

13

1. A compound of formula (I), (II) or (III)

wherein Q is

wherein R is independently H or C₁-C₄alkyl; D is O or NR₃; in formula (I) m and n independently are a number 0 or 1 wherein at least one of both is 1; if in formula (I) m=0 and n=1 X is

 wherein * denotes where the group is attached to the oxygen atom; A is O or NR₃; B₁ is C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups, C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl) or phenylene; additionally -A-B₁- can be a direct bond; or if A is —O— and D is NR₃, B₁ can be a direct bond; or if A is NR₃ and D is O or NR₃, B₁ can be a direct bond; E is a direct bond or a —C(O)— group; R₁, R₂ and R₃ are independently H, C₁-C₁₈alkyl, which is unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl), C₅-C₇cycloalkyl, which is unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl), phenyl, which is unsubstituted or substituted by C₁-C₈alkoxy, C₁-C₈alkyl, halogen or a group —COO(C₁-C₁₈alkyl); the group

 is

A is as defined above; and if A is O, E₁ is —CH₂— if A is NR₃, E₁ is —C(O)—, —CH₂— or a direct bond; R₄, R₅, R₆ are independently C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₇-C₉phenylalkyl or phenyl; R₇, R₈ are independently H, C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₇-C₉phenylalkyl or C₁-C₁₈acyl; L is a direct bond, O or NR₇; R₉, R₁₀ are independently H or C₁-C₁₈alkoxy, if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acyl or N(R₃)₂; or R₉ and R₁₀ together with the C-atom to which they are bonded form a cyclic ketale group

 wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or —CH₂—O—(C₁-C₁₈)acyl; or R₉ and R₁₀ together form the group ═O, or ═N-A-R₇; R₁₁, R₁₂, R₁₃ and R₁₄ are independently of each other C₁-C₄alkyl; if in formula (I) m=1 and n=1 X is as defined above; the group

 is

 wherein A and B₁ are as defined above; if in formula (I) m=1 and n=0 X is

 wherein A is O, NR₃ or a direct bond and E, R₁ and R₂ are as defined above; B₃ is H, C₁-C₂₅alkyl, which may be interrupted by O or NR₃ groups, C₅-C₇cycloalkyl, which can contain O and or NR₃ groups in the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl) or C₁-C₁₈alkoxy or phenyl; the group

 is

 wherein A and B₁ are as defined above; in formula (II) X is

 wherein * denotes where X is attached to the oxygen atom and A, B₁, E, R₁ and R₂ are as defined above; the group

 is

 wherein A is as defined above; L₁ is a divalent group derived from an aliphatic dicarboxylic acid having 2 to 18 carbon atoms from an aromatic dicarboxylic acid or from an aliphatic-aromatic dicarboxylic acid; in formula (III) X₁ is a group

 wherein B₂ is a direct bond, C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups, C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl) or phenylene, wherein when B₂ is a direct bond one A is O and the other is NR₃; A, B₁, R₁ and R₂ are as defined above and the group

 is


2. A compound according to claim 1 of formula (I), (II) or (III) wherein Q is

R is independently H or C₁-C₄alkyl; and D is O or NR₃.
 3. A compound according to claim 1 of formula (I), (II) or (III)

wherein Q is

wherein R is independently H or C₁-C₄alkyl; D is O or NR₃; in formula (I) m and n independently are a number 0 or 1 wherein at least one of both is 1; if in formula (I) m=0 and n=1 X is

 wherein * denotes where the group is attached to the oxygen atom; A is O or NR₃; B₁ is C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups, C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl) or phenylene; additionally -A-B₁- can be a direct bond; or if A is —O— and D is NR₃, B₁ can be a direct bond; or if A is NR₃ and D is O or NR₃, B₁ can be a direct bond; E is a direct bond or a —C(O)— group; R₁, R₂ and R₃ are independently H, C₁-C₁₈alkyl, which is unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl), C₅-C₇cycloalkyl, which is unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl), phenyl, which is unsubstituted or substituted by C₁-C₈alkoxy, C₁-C₈alkyl, halogen or a group —COO(C₁-C₁₈alkyl); the group

 is

 wherein A is as defined above; and if A is O, E₁ is —CH₂— if A is NR₃, E₁ is —C(O)—, —CH₂— or a direct bond; R₇ is H, C₁-C₁₈alkyl, C₅-C₇cycloalkyl, C₇-C₉phenylalkyl or C₁-C₁₈acyl; R₉, R₁₀ are independently H or C₁-C₁₈alkoxy, if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acyl or N(R₃)₂; or R₉ and R₁₀ together with the C-atom to which they are bonded form a cyclic ketale group

 wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or —CH₂—O—(C₁-C₁₈)acyl; or R₉ and R₁₀ together form the group ═O, or ═N-A-R₇; if in formula (I) m=1 and n=1 X is as defined above; the group

 is

 wherein A and B₁ are as defined above; if in formula (I) m=1 and n=0

 wherein A is O, NR₃ or a direct bond and E, R₁ and R₂ are as defined above; B₃ is H, C₁-C₂₅alkyl, which may be interrupted by O or NR₃ groups, C₅-C₇cycloalkyl, which can contain O and or NR₃ groups in the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl) or C₁-C₁₈alkoxy or phenyl; the group

 is

 wherein A and B₁ are as defined above; in formula (II) X is

 wherein * denotes where X is attached to the oxygen atom and A, B₁, E₁ R₂ and R₂ are as defined above; the group

 is

 wherein A is as defined above; L₁ is a divalent group derived from an aliphatic dicarboxylic acid having 2 to 18 carbon atoms from an aromatic dicarboxylic acid or from an aliphatic-aromatic dicarboxylic acid; in formula (III) X₁ is a group

 wherein B₂ is a direct bond, C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups, C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl) or phenylene, wherein when B₂ is a direct bond one A is O and the other is NR₃; A, B₁, R₁ and R₂ are as defined above and the group

 is


4. A compound according to claim 1 of formula (Ia)

wherein Q is

 wherein R is independently H or C₁-C₄alkyl; X is

 wherein * denotes where X is attached to the oxygen atom; A is O or NR₃; B₁ is C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups, C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl) or phenylene; additionally -A-B₁- can be a direct bond; or if A is —O— and D is NR₃, B₁ can be a direct bond; or if A is NR₃ and D is O or NR₃, B₁ can be a direct bond; E is a direct bond; R₁, R₂ are H or CH₃; R₃ is H, C₁-C₁₈alkyl, C₅-C₆cycloalkyl or phenyl; the group

 is

 wherein A is as defined above; and if A is O, E₁ is —CH₂— if A is NR₃, E₁ is —C(O)—, —CH₂— or a direct bond; R₄, R₅, are methyl; R₇, R₈ are independently H, C₁-C₁₈alkyl, C₅-C₇cycloalkyl, benzyl or C₁-C₁₈acyl; L is a direct bond, O or NR₇; R₉, R₁₀ are independently H or C₁-C₁₈alkoxy, if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acyl or N(R₃)₂; or R₉ and R₁₀ together with the C-atom to which they are bonded form a cyclic ketale group

wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or —CH₂—O—(C₁-C₁₈)acyl; or R₉ and R₁₀ together form the group ═O, or ═N-A-R₇; R₁₁, R₁₂, R₁₃ and R₁₄ are independently of each other C₁-C₄alkyl.
 5. A compound according to claim 4 of formula (Ia)

wherein Q is

 wherein R is H or C₁-C₄alkyl; X is

 wherein * denotes where X is attached to the oxygen atom; A is O or NR₃; B₁ is C₁-C₂₅alkylene, which may be interrupted by O or NR₃ groups, C₅-C₇cycloalkylene which can contain O and or NR₃ groups in the ring, which both are unsubstituted or substituted by C₁-C₈alkoxy, halogen or a group —COO(C₁-C₁₈alkyl) or phenylene; additionally -A-B₁- can be a direct bond; or if A is —O— and D is NR₃, B₁ can be a direct bond; or if A is NR₃ and D is O or NR₃, B₁ can be a direct bond; E is a direct bond; R₁, R₂ are H or CH₃; R₃ is H, C₁-C₁₈alkyl, C₅-C₆cycloalkyl or phenyl; the group

 is

 wherein A is as defined above; and if A is O, E₁ is —CH₂— if A is NR₃, E₁ is —C(O)—, —CH₂— or a direct bond; R₇ is H, C₁-C₁₈alkyl, C₅-C₇cycloalkyl, benzyl or C₁-C₁₈acyl; R₉, R₁₀ are independently H or C₁-C₁₈alkoxy, if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃—(C₁-C₁₈)acyl or N(R₃)₂; or R₉ and R₁₀ together with the C-atom to which they are bonded form a cyclic ketale group

 wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or —CH₂—O—(C₁-C₁₈)acyl; or R₉ and R₁₀ together form the group ═O, or ═N—O—R₇; R₁₁, R₁₂, R₁₃ and R₁₄ are independently of each other C₁-C₄alkyl.
 6. A compound according to claim 5 of formula (Ia)

wherein Q is

X is

 wherein * denotes where X is attached to the oxygen atom; A is O or NR₃; B₁ is C₁-C₁₈alkylene, or phenylene; R₁, R₂ are H or CH₃; R₃ is H, C₁-C₄alkyl or phenyl; the group

 is

R₉, R₁₀ are independently H or C₁-C₁₈alkoxy, or if R₉ is H, R₁₀ is additionally OH, —O—(C₁-C₁₈)acyl, —NR₃-(C₁-C₁₈)acyl or N(R₃)₂; or R₉ and R₁₀ together with the C-atom to which they are bonded form a cyclic ketale group

 wherein k is 0, 1 or 2 and R₁₅ is C₁-C₁₈alkyl, —CH₂—OH or —CH₂—O—(C₁-C₁₈)acyl; or R₉ and R₁₀ together form the group ═O, or ═N—O—R₇; R₁₁, R₁₂, R₁₃ and R₁₄ are independently of each other C₁-C₄alkyl.
 7. A compound according to claim 6 of formula (Ia)

wherein Q is

X is

 wherein * denotes where X is attached to the oxygen atom; A is O or NR₃; B₁ is C₁-C₄alkylene, or phenylene; R₁, R₂ are H or CH₃; R₃ is H, C₁-C₄alkyl or phenyl; the group

 is


8. A compound according to claim 1, which is a) Acrylic acid 2-[2-(2,6-diethyl-4-hydroxy-2,3,6-trimethyl-piperidin-1-yloxy)-propionyloxy]-ethyl ester b) Acrylic acid 2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionyloxy]-ethyl ester c) Acrylic acid 2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-2-methyl-propionylamino]ethyl ester d) Acrylic acid 1-(1-{6-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionylamino]-hexylcarbamoyl}-ethoxy)-2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl ester e) 2-Methyl-acrylic acid 2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionylamino]-ethyl ester f) Acrylic acid 2-[2-(4-tert-butyl-2,2-diethyl-6,6-dimethyl-3-oxo-piperazin-1-yloxy)-propionylamino]-ethyl ester g) Acrylic acid 2-(2-{N-tert-butyl-N-[1-(diethoxy-phosphoryl)-2,2-dimethyl-propyl]-aminooxy}propionylamino)-ethyl ester h) Acrylic acid 2-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionylamino]-ethyl ester i) Terephthalic acid bis-{1-[1-(2-acryloyloxy-ethylcarbamoyl)-ethoxy]-2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl}ester j) 2-Methyl-acrylic acid 2-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperidin-1-yloxy)-propionyloxy]-ethyl ester k) 2-Methyl-acrylic acid 1-[1-(2-acryloyloxy-ethoxycarbonyl)-ethoxy]-2,6-diethyl-2,3,6-trimethyl-piperidin-4-yl ester l) Acrylic acid 2-[2-(4-acryloyloxy-2,6-diethyl-2,3,6-trimethyl-piperidin-1-yloxy)-propionyloxy]-ethyl ester m) Acrylic acid 2-{(2-acryloyloxy-ethyl)-[2-(2,6-diethyl-2,3,6-trimethyl-4-oxo-piperdin-1-yloxy)-propionyl]-amino}-ethyl ester.
 9. A polymerizable composition comprising a) at least one ethylenically unsaturated monomer; b) a radical polymerization initiator; and c) a compound of formula (I), (II) or (III) according to claim
 1. 10. A polymerizable composition according to claim 9 wherein the ethylenically unsaturated monomer is selected from the group consisting of ethylene, propylene, n-butylene, i-butylene, styrene, substituted styrene, conjugated dienes, acrolein, vinyl acetate, vinylpyrrolidone, vinylimidazole, maleic anhydride, (alkyl)acrylic acidanhydrides, (alkyl)acrylic acid salts, (alkyl)acrylic esters, (alkyl)acrylonitriles, (alkyl)acrylamides, vinyl halides or vinylidene halides.
 11. A polymerizable composition according to claim 10 wherein the ethylenically unsaturated monomer is a compound of formula CH₂═C(R_(a))—(C=Z)-R_(b), wherein Z is O or S; R_(a) is hydrogen or C₁-C₄alkyl; R_(b) is NH₂, O⁻(Me⁺), glycidyl, unsubstituted C₁-C₁₈alkoxy, C₂-C₁₀₀alkoxy interrupted by at least one N and/or O atom, or hydroxy-substituted C₁-C₁₈alkoxy, unsubstituted C₁-C₁₈alkylamino, di(C₁-C₁₈alkyl)amino, hydroxy-substituted C₁-C₁₈alkylamino or hydroxy-substituted di(C₁-C₁₈alkyl)amino, —O—CH₂—CH₂—N(CH₃)₂ or —O—CH₂—CH₂—N⁺H(CH₃)₂ An⁻; An⁻ is a anion of a monovalent organic or inorganic acid; Me is a monovalent metal atom or the ammonium ion.
 12. A polymerizable composition according to claim 9 wherein the radical polymerization initiator is a azo compound, a peroxide, a perester or a hydroperoxide.
 13. A process for preparing an oligomer, a cooligomer, a polymer or a copolymer (block, random or graft) by free radical polymerization of at least one ethylenically unsaturated monomer or oligomer, which comprises (co)polymerizing the monomer or monomers/oligomers in the presence of a) a free radical initiator; and b) a compound of formula (I), (II) or (III) according to claim
 1. 14. A process according to claim 13 wherein polymerization is carried out by applying heat or electromagnetic radiation from microwaves to γ-radiation.
 15. A process according to claim 13 wherein the polymerization is carried out by heating and takes place at a temperature between 0° C. and 160° C.
 16. A process according to claim 13 wherein the amount of component b) is from 1% to 100% by weight, based on the weight of the sum of all ethylenically unsaturated compounds.
 17. A polymeric or oligomeric macroinitiator obtainable by a process according to claim
 13. 18. A process for preparing a comb, star, tapered or branched polymer or copolymer by controlled free radical polymerization (CFRP), which comprises polymerizing at least one ethylenically unsaturated monomer in the presence of the polymeric macroinitiator obtainable in a process according to claim
 13. 19. A process according to claim 18 wherein the polymerization is carried out by heating and takes place at a temperature between 80° C. and 160° C.
 20. Use of a polymeric macroinitiator obtainable in a process according to claim 13, as radical initiator for the polymerization of ethylenically unsaturated monomers. 